Method for permanently shaping keratin fibers, and agents

ABSTRACT

A process for permanently deforming keratin fibers and compositions suitable for use in this process are provided. The process includes treating keratin fibers, before and/or after mechanically deforming the keratin fibers, with an aqueous reducing composition containing a keratin reducing substance, rinsing the keratin fibers with a rinse after contact with the reducing composition, and applying to the keratin fibers an aqueous fixing composition containing an oxidizing agent, where at least one of the reducing composition, the fixing composition, or the rinse is in the form of a two-phase or multiphase system. The two phase or multiphase system contains at least one oil component and/or at least one alcohol having limited miscibility with water and is capable of being converted at least temporarily with mechanical agitation into a homogeneous system for application to hair.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 U.S.C. § 371of international application PCT/EP99/05785 filed on Aug. 10, 1999, theinternational application not being published in English. Thisapplication also claims priority under 35 U.S.C. §119 to DE 199 30 769.5filed on Jul. 3, 1999.

BACKGROUND OF THE INVENTION

This invention relates to a process for the permanent deforming ofkeratin fibers, more especially human hair, by reductive cleavage andoxidative re-establishment of disulfide bonds of the keratin and topreparations suitable for this process.

The permanent deforming of keratin fibers is normally carried out bymechanically deforming the fibers and fixing the deformation by suitableauxiliaries. Before and/or after their deformation, the fibers aretreated with an aqueous preparation of a keratin-reducing substance and,after a contact time, are rinsed with water or with an aqueous solution.In a second step, the fibers are treated with an aqueous preparation ofan oxidizing agent. After a certain contact time, the oxidizing agent isalso rinsed out and the mechanical deforming aids (curlers, rollers) areremoved from the fibers.

The aqueous preparation of the keratin reducing agent is normallyalkalized so that, on the one hand, enough of the thiol functions aredeprotonated and, on the other hand, the fiber swells so that thekeratin-reducing substance is able to penetrate deeply into the fiber.The keratin-reducing substance splits some of the disulfide bonds of thekeratin to —SH groups, so that the peptide linkage is loosened and,through the stretching of the fibers by their mechanical deformation,the keratin structure is re-oriented. Under the influence of theoxidizing agent, disulfide bonds are re-established and, in this way,the deformation which the keratin structure has undergone is fixed. Aknown process of the type in question is the permanent waving of humanhair. This process may be applied both to produce curls and waves instraight hair and to straighten curly hair.

Unfortunately, a negative side effect of the permanent waving of haircarried out in this way is that the hair often becomes brittle and dull.In addition, other properties, such as wet and dry combability, feel,flexibility, softness, luster and tear strength, are also adverselyaffected in many cases.

Accordingly, there has been no shortage of attempts in the past toremedy this situation.

A corresponding modification of the reducing solution leads to generallyunsatisfactory waving performance. Although the addition of knownadditives, such as structurants, polymers, film formers and crosslinkingresins, or the adjustment of the preparation to a neutral or mildlyacidic pH can reduce the damage done to the hair, the hair remains moreor less weakened in its structure. Although care of the hair by furtheraftertreatments can again improve the properties of the hair, it doestake more time and, in general, involves the use of at least one otherformulation.

Accordingly, there was still a need to find a process for permanentlydeforming keratin fibers in which the unwanted side effects mentionedwould be further reduced or eliminated altogether.

It has now surprisingly been found that a significant improvement in theproperties of deformed keratin fibers, such as improved combability andcondition, can be achieved if at least one preparation used during thedeforming process is formulated as a multiphase preparation and containsspecial compounds.

SUMMARY OF THE INVENTION

Accordingly, the present invention relates to a process for thepermanent deforming of keratin fibers in which the fibers are treatedbefore and/or after mechanical deforming with an aqueous preparation ofa keratin-reducing substance, rinsed with a first rinse after a certaincontact time, fixed with an aqueous preparation of an oxidizing agentand rinsed and optionally aftertreated, again after a certain contacttime, characterized in that at least one of the two aqueous preparationsor the first rinse is present in the form of a two-phase or multiphasesystem which contains at least one oil component and/or at least onealcohol having only limited miscibility with water and which, forapplication to the fibers, is converted by mechanical agitation into ahomogeneous system.

DETAILED DESCRIPTION OF THE INVENTION

The following terms are used hereinafter:

-   -   “wave lotion” for the aqueous preparation of the        keratin-reducing substance,    -   “intermediate rinse” for the first rinse and    -   “fixing agent” for the aqueous preparation of the oxidizing        agent.

In the process according to the invention, the wave lotion, theintermediate rinse and/or the fixing agent is/are formulated as atwo-phase or multiphase system. Two-phase and multiphase systems used inaccordance with the invention are systems in which at least two separatecontinuous phases are present. Examples of such systems are preparationswhich contain the following phases:

-   -   an aqueous phase and a non-aqueous phase which are present        separately from one another    -   an aqueous phase and two non-aqueous immiscible phases which are        separately present    -   an oil-in-water emulsion and a separate non-aqueous phase    -   a water-in-oil emulsion and a separate aqueous phase.

No two-phase systems in the context of the present invention are systemsin which there is only one continuous phase such as, for example, pureoil-in-water or water-in-oil emulsions.

The formulations containing two-phase or multiphase systems used in theprocess according to the invention only develop their full effect whenthey are applied to the keratin fibers in homogeneous form. To this end,the formulations are converted into homogeneous systems by mechanicalaction, for example by simple manual shaking of the containeraccommodating them. In order to ensure homogeneous application to thekeratin fibers, this homogeneous state must remain intact for asufficient time before the individual phases re-form. For the teachingaccording to the present invention, it has proved to be sufficient forthis homogeneous state to remain stable for at least 20 seconds and,more particularly, at least 30 seconds before a boundary layer and hencethe formation of the individual phases is visible to the observer.

Besides water, the two-phase and multiphase systems used in accordancewith the invention contain at least one oil component and/or at leastone alcohol having only limited miscibility with water as a compulsorycomponent(s).

Oil components suitable for use in accordance with the invention are, inprinciple, any oils and fatty compounds and mixtures thereof with solidparaffins and waxes. Preferred oil components are those which have asolubility in water at 20° C. of less than 1% by weight and, moreparticularly, less than 0.1% by weight. The melting point of theindividual oil or fatty components is preferably below about 40° C. Oilcomponents which are liquid at room temperature, i.e. below 25° C., canbe of particular advantage for the purposes of the invention. However,where several oil and fatty components and optionally solid paraffinsand waxes are used, it is generally even sufficient if the mixture ofthe oil and fatty components and optionally paraffins and waxes meetsthese requirements.

A preferred group of oil components are vegetable oils. Examples of suchoils are apricot kernel oil, avocado oil, sunflower oil, olive oil,soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheatgerm oil, peach kernel oil and the liquid fractions of coconut oil.However, other triglycerides, such as the liquid fractions of beeftallow, and synthetic triglyceride oils are also suitable.

Another particularly preferred group of oil components suitable for usein accordance with invention are liquid paraffin oils and synthetichydrocarbons and also di-n-alkyl ethers containing a total of 12 to 36carbon atoms and, more particularly, 12 to 24 carbon atoms such as, forexample, di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether,di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether,n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecylether and n-hexyl-n-undecyl ether and di-tert.butyl ether, diisopentylether, di-3-ethyldecyl ether, tert.butyl-n-octyl ether,isopentyl-n-octyl ether and 2-methylpentyl-n-octyl ether. The compoundsobtainable as commercial products, 1,3-di-(2-ethylhexyl)-cyclohexane(Cetiol® S) and di-n-octyl ether (Cetiol® OE), can be preferred.

Other oil components suitable for use in accordance with the inventionare fatty acid and fatty alcohol esters. The monoesters of fatty acidswith alcohols containing 3 to 24 carbon atoms are preferred. This groupof compounds are products of the esterification of fatty acidscontaining 8 to 24 carbon atoms such as, for example, caproic acid,caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid,isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid,stearic acid, isostearic acid, oleic acid, elaidic acid, petroselicacid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid,gadoleic acid, behenic acid and erucic acid and the technical mixturesthereof obtained, for example, in the pressure hydrolysis of naturalfats and oils, in the reduction of aldehydes from Roelen's oxosynthesisor in the dimerization of unsaturated fatty acids, with alcohols suchas, for example, isopropyl alcohol, glycerol, caproic alcohol, caprylicalcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol,isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleylalcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidylalcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol,elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenylalcohol, erucyl alcohol and brassidyl alcohol and the technical mixturesthereof obtained, for example, in the high-pressure hydrogenation oftechnical methyl esters based on fats and oils or aldehydes fromRoelen's oxosynthesis and as monomer fraction in the dimerization ofunsaturated fatty alcohols. According to the invention, isopropylmyristate, isononanoic acid-C₁₆₋₁₈-alkyl ester (Cetiol® SN), stearicacid-2-ethylhexyl ester (Cetiol® 868), cetyl oleate, glyceroltricaprylate, cocofatty alcohol caprate/caprylate and n-butyl stearateare particularly preferred.

Other oil components suitable for use in accordance with the inventionare dicarboxylic acid esters, such as di-n-butyl adipate,di-(2-ethylhexyl)-adipate, di-(2-ethylhexyl)-succinate and diisotridecylazelate, and diol esters, such as ethylene glycol dioleate, ethyleneglycol diisotri-decanoate, propylene glycol di-(2-ethylhexanoate),propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate, and complex esterssuch as, for example, diacetyl glycerol monostearate.

Finally, other oil components preferably used for the purposes of theinvention are silicone oils, more particularly dialkyl and alkylarylsiloxanes such as, for example, dimethyl polysiloxane and methylphenylpolysiloxane and alkoxylated and quaternized analogs thereof. Examplesof such silicone oils are the products marketed by Dow Corning under thenames of DC 190, DC 200 and DC 1401 and the commercial products DC 344and DC 345 of Dow Corning, Q2-7224 (manufacturer: Dow Corning; astabilized trimethyl silyl amodimethicone), Dow Corning® 929 emulsion(containing a hydroxyl amino-modified silicone which is also known asAmodimethicone), SN-2059 (manufacturer: General Electric), SLM-55067(manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufacturer: Th.Goldschmidt; diquaternary polydimethyl siloxanes, Quaternium-80).

Finally, other oil components suitable for use in accordance with theinvention are the dialkyl carbonates described in detail in DE-OS 197101 54 to which reference is expressly made. Dioctyl carbonates, moreespecially di-2-ethylhexyl carbonate, are preferred oil components forthe purposes of the present invention.

According to the invention, alcohols having only limited miscibilitywith water may be used as an alternative to or in addition to the oilcomponents mentioned.

“Alcohols having only limited miscibility with water” are understood tobe alcohols of which no more than 10% by weight dissolves in water at20° C. (based on the weight of the water).

In many cases, triols and, in particular, diols have proved to beparticularly suitable for the purposes of the invention. Alcoholscontaining 4 to 20 and more particularly 4 to 10 carbon atoms may beused in accordance with the invention. The alcohols used in accordancewith the invention may be saturated or unsaturated and linear, branchedor cyclic. Examples of alcohols suitable for use in accordance with theinvention are 1-butanol, cyclohexanol, 1-pentanol, decanol, octanol,octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleylalcohol, erucyl alcohol, ricinolyl alcohol, stearyl alcohol, isostearylalcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidylalcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenylalcohol and behenyl alcohol and Guerbet alcohols thereof (this list ispurely exemplary and is not intended to limit the invention in any way).However, the fatty alcohols emanate from preferably natural fatty acids,normally being obtained from the esters of the fatty acids by reduction.According to the invention, it is also possible to use the fatty alcoholcuts which are produced by reduction of naturally occurringtriglycerides, such as beef tallow, palm oil, peanut oil, rapeseed oil,cottonseed oil, soybean oil, sunflower oil and linseed oil, or fattyacid esters formed from the transesterification products thereof withcorresponding alcohols and which therefore represent a mixture ofdifferent fatty alcohols.

According to the invention, preferred alcohols are2-ethylhexane-1,3-diol, 1-butanol, cyclohexanol, 1-pentanol andbutane-1,2-diol. 2-Ethylhexane-1,3-diol, 1-butanol and cyclohexanol areparticularly preferred.

The aqueous and non-aqueous phases are present in the formulations usedin the process according to the invention in ratios by weight of 1:200to 1:1, preferably 1:40 to 1:5 and more preferably 1:20 to 1:10. Incases where several non-aqueous phases are present, these figures applyto the non-aqueous phases as a whole.

The teaching according to the invention also encompasses thoseembodiments of the process according to the invention in which themultiphase preparation is made up just before use from two or moreseparately produced starting preparations. This embodiment can bepreferred in the case of highly incompatible components.

The present invention also relates to the preparations used to carry outthe process according to the invention.

In a process for permanently deforming keratin fibers, thesepreparations are used either to carry out the reducing step, to carryout the oxidizing step or for rinsing after the reducing step and, inprinciple, may contain any of the ingredients typical of suchpreparations providing the requirements according to the invention(presence of the two-phase or multiphase system and rapid miscibility)are satisfied.

The process according to the invention is preferably used forpermanently waving or straightening human hair.

In one preferred embodiment of the process according to the invention,the wave lotion is formulated in the form of the two-phase or multiphasesystem mentioned above. It has surprisingly been found that wave lotionsformulated in this way have a much stronger wave effect for the sameamount of the particular keratin-reducing components. Similarly, thewaving performance achieved with a wave lotion which has not beenformulated in accordance with the invention can be achieved with onewhich has despite a distinct reduction in the amount of keratin-reducingsubstance, which is beneficial both to the hair and to the scalp.

In addition, it has been found that, by formulating the wave lotion as atwo-phase or multiphase system, the difficulties involved in perfumingcan be distinctly reduced. However, perfuming is virtually indispensablebecause the perfume note of the compulsory ingredients of the wavelotion (keratin-reducing thio compounds, optionally alkalis, such asammonia or alkanolamines) is not acceptable to most users. The problemis that most of the perfume components in these wave lotions are notstable in storage. Accordingly, the choice of perfume notes for suchlotions is seriously restricted. It has now surprisingly been foundthat, where the two-phase or multiphase systems according to theinvention are used, a number of other perfume components can be stablyincorporated in the wave lotion. Additional perfume components have alsobeen found to lend themselves to stable incorporation in fixingsolutions made up in accordance with the invention. In the case ofintermediate rinses containing the two-phase and multiphase systemsaccording to the invention, it has been found that there is often noneed to use emulsifiers or solubilizers for incorporating the perfumecomponents.

Accordingly, in a second embodiment, the present invention relates to apreparation for carrying out the reducing step of a process forpermanently deforming keratin fibers containing a keratin-reducingsubstance and typical ingredients, characterized in that it is presentin the form of a two-phase or multiphase system which contains at leastone oil component and/or at least one alcohol having only limitedmiscibility with water and which can be converted by mechanical actioninto a homogeneous system.

The wave lotions according to the invention contain mercaptans known askeratin-reducing substances as a compulsory component. Examples of suchcompounds are thioglycolic acid, thiolactic acid, thiomalic acid,mercaptoethane sulfonic acid and salts and esters thereof, cysteamine,cysteine, Bunte salts and salts of sulfurous acid. The alkali metal orammonium salts of thioglycolic acid and/or thiolactic acid and freeacids are particularly suitable. They are used in the wave lotions inconcentrations of preferably 0.5 to 1.0 mol/kg at a pH value of 5 to 12and, more particularly, 7 to 9.5. In order to adjust this pH value, thewave lotions according to the invention normally containing alkalizingagents, such as ammonia, alkali metal and ammonium carbonates andhydrogen carbonates, or organic amines, such as monoethanolamine.

In addition, the wave lotions according to the invention may containcomponents which boost their waving power such as, for example,

-   -   heterocyclic compounds, such as imidazole, pyrrolidine,        piperidine, dioxolane, dioxane, morpholine and piperazine, and        derivatives of these compounds such as, for example, C₁₋₄ alkyl        derivatives, C₁₋₄ hydroxy-alkyl derivatives and C₁₋₄ aminoalkyl        derivatives. Preferred substituents which may be positioned both        at carbon atoms and at nitrogen atoms of the heterocyclic ring        systems are methyl, ethyl, β-hydroxyethyl and β-aminoethyl        groups. According to the invention, preferred derivatives of        heterocyclic compounds are, for example, 1-methyl imidazole,        2-methyl imidazole, 4(5)-methyl imidazole, 1,2-dimethyl        imidazole, 2-ethyl imidazole, 2-isopropyl imidazole, N-methyl        pyrrolidine, 1-methyl piperidine, 4-methyl piperidine, 2-ethyl        piperidine, 4-methyl morpholine, 4-(2-hydroxyethyl)-morpholine,        1-ethyl piperazine, 1-(2-hydroxyethyl)-piperazine,        1-(2-aminoethyl)-piperazine. According to the invention, other        preferred imidazole derivatives are biotin, hydantoin and        benzimidazole. Imidazole is most particularly preferred.    -   Amino acids such as, in particular, arginine, citrulline,        histidine, ornithine and lysine. The amino acids may be used        both as free amino acid and as salts, for example as        hydrochlorides. Oligopeptides of on average 2 to 3 amino acids,        which have a high percentage content (>50%, more        particularly >70%) of the amino acids mentioned, have also        proved to be suitable for use in accordance with the invention.        According to the invention, arginine and arginine salts and        arginine-rich oligopeptides are particularly preferred.    -   Diols such as, for example, 2-ethylhexane-1,3-diol,        butane-1,3-diol, butane-1,4-diol, propane-1,2-diol,        propane-1,3-diol, neopentyl glycol and ethylene glycol.        1,3-Diols, more especially 2-ethylhexane-1,3-diol and        butane-1,3-diol, have proved to be particularly suitable.

Further information on these components which boost waving power can befound in DE-OS 44 36 065 and EP-B1 36057, to which reference is herebyexpressly made.

The compounds which boost waving power may be present in the wavelotions according to the invention in quantities of 0.5 to 5% by weight,based on the wave lotion as a whole. Quantities of 1 to 4% by weightand, in the case of the diols, 0.5 to 3% by weight have proved to besufficient so that these quantities are particularly preferred.

In a third embodiment, the present invention relates to a preparationfor carrying out the oxidizing step of a process for permanentlydeforming keratin fibers containing an oxidizing agent and typicalingredients, characterized in that it is present in the form of atwo-phase or multiphase system which contains at least one oil componentand/or at least one alcohol having only limited miscibility with waterand which can be converted by mechanical action into a homogeneoussystem.

A compulsory ingredient of the fixing preparation according to theinvention are oxidizing agents, for example sodium bromate, potassiumbromate, hydrogen peroxide, and the stabilizers normally used tostabilize aqueous hydrogen peroxide preparations. The pH value of suchaqueous hydrogen peroxide preparations, which normally contain about 0.5to 15% by weight and, in ready-to-use form, generally about 0.5 to 3% byweight of H₂O₂, is preferably in the range from 2 to 6 and morepreferably in the range from 2 to 4. It is adjusted by inorganic acids,preferably phosphoric acid. Bromate-based fixing preparations containthe bromates in concentrations of normally 1 to 10% by weight, the pHvalue of the solutions being adjusted to pH 4-7. Enzyme-based (forexample peroxide-based) fixing preparations containing only smallquantities, if any, of oxidizing agents, more especially H₂O₂, are alsosuitable.

In a fourth embodiment, the present invention relates to a preparationfor rinsing after the reducing step of a process for permanentlydeforming keratin fibers containing typical ingredients, characterizedin that it is present in the form of a two-phase or multiphase systemwhich contains at least one oil component and/or at least one alcoholhaving only limited miscibility with water and which can be converted bymechanical action into a homogeneous system.

It has also been found to be of advantage for the preparations accordingto the invention to contain a hair-care ingredient selected from proteinhydrolyzates and derivatives thereof.

Suitable protein hydrolyzates are, in particular, elastin, collagen,keratin, milk protein, silk protein, soya protein, almond protein, peaprotein, potato protein, oat protein, corn protein and wheat proteinhydrolyzates. According to the invention, products on a vegetable basiscan be preferred.

Suitable derivatives of the protein hydrolyzates are, in particular,condensation products thereof with fatty acids and fatty acid mixtures,such as oleic acid, myristic acid, undecylenic acid, cocofatty acid andabietic acid. The condensation products may also be present in the formof salts, more especially sodium, potassium and triethanolamine salts.

Other suitable derivatives are quaternized protein hydrolyzates.Examples of this class of compounds are the products commerciallyavailable under the names of Lamequat®L (CTFA name: LauryldimoniumHydroxypropylamino Hydrolyzed Animal Protein; Grünau), Croquat®WKP andGluadin®WQ. The last of these products, which is vegetable-based, can bepreferred. The protein derivatives are present in the preparationsaccording to the invention in quantities of preferably 0.1 to 10% byweight and more preferably 0.1 to 5% by weight, based on the preparationas a whole.

In addition, the preparations according to the invention contain atleast one conditioning agent.

Preferred conditioning agents are cationic polymers which are generallypolymers that contain a quaternary nitrogen atom, for example in theform of an ammonium group. Preferred cationic polymers are, for example,

-   -   the quaternized cellulose derivatives commercially available        under the names of Celquat® and Polymer JR®. The compounds        Celquat® H 100, Celquat® L 200 and Polymer JR® 400 are preferred        quaternized cellulose derivatives;    -   polysiloxanes containing quaternary groups;    -   polymeric dimethyl diallyl ammonium salts and copolymers thereof        with esters and amides of acrylic acid and methacrylic acid. The        products commercially available under the names of Merquat® 100        (poly(dimethyl diallylammonium chloride)) and Merquat® 550        (dimethyl diallylammonium chloride/acrylamide copolymer) are        examples of such cationic polymers;    -   copolymers of vinyl pyrrolidone with quaternized derivatives of        dialkylaminoacrylate and methacrylate such as, for example,        vinyl pyrrolidone/dimethylaminomethyl methacrylate copolymers        quaternized with diethyl sulfate. Such compounds are        commercially available under the name of Gafquat® 734 and        Gafquat® 755.    -   The vinyl pyrrolidones/vinyl imidazolinium methochloride        copolymers commercially available under the name of Luviquat®;    -   quaternized polyvinyl alcohol;        and the polymers containing quaternary nitrogen atoms in the        main polymer chain known under the names of    -   Polyquaternium 2,    -   Polyquaternium 17,    -   Polyquaternium 18 and    -   Polyquaternium 27.

Other suitable conditioning agents are so-called amphopolymers.Amphopolymers are amphoteric polymers, i.e. polymers which contain bothfree amino groups and free —COOH or —SO₃H groups in the molecule andwhich are capable of forming inner salts, zwitterionic polymers whichcontain quaternary ammonium groups and —COOH⁻ or —SO₃ ⁻ groups in themolecule and polymers which contain —COOH or SO₃H groups and quaternaryammonium groups. One example of an amphopolymer suitable for use inaccordance with the invention is the acrylate resin commerciallyavailable as Amphomer® which is a copolymer of tert.butylaminoethylmethacrylate, N-(1,1,3,3-tetramethylbutyl)-acrylamide and two or moremonomers from the group consisting of acrylic acid, methacrylic acid andsimple esters thereof. Other preferred amphopolymers consist ofunsaturated carboxylic acids (for example acrylic and methacrylic acid),cationically derivatized unsaturated carboxylic acids (for exampleacrylamidopropyl trimethyl ammonium chloride) and optionally other ionicor nonionic monomers of the type disclosed, for example, in DE-OS 39 29973 and the prior art literature cited therein. According to theinvention, terpolymers of acrylic acid, methyl acrylate andmethacrylamidopropyl trimonium chloride, which are commerciallyavailable under the name of Merquat® 2001 N, and the commercial productMerquat® 280 are particularly preferred amphopolymers.

The cationic or amphoteric polymers are present in the preparationsaccording to the invention in quantities of preferably 0.1 to 5% byweight, based on the preparation as a whole.

Silicone oils and silicone gums suitable as conditioning agents are, inparticular, dialkyl and alkylaryl siloxanes, such as for exampledimethyl polysiloxane and methylphenyl polysiloxane, and alkoxylated andquaternized analogs thereof. Examples of such silicones are the productsmarketed by Dow Corning under the names of DC 190, DC 200 and DC 1401and the commercial product Fancorsil® LIM-1.

According to the invention, other suitable conditioning agents arecationic silicone oils such as, for example, the commercially availableproducts Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilyl amodimethicone), Dow Corning®) 929 emulsion (containing a hydroxylamino-modified silicone which is also known as Amodimethicone), SN-2059(manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) andAbil® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt;

-   -   diquaternary polydimethyl siloxanes, Quaternium-80). A suitable        anionic silicone oil is the product Dow Corning® 1784.

Examples of the cationic surfactants suitable for use as conditioningagents in the preparations according to the invention are, inparticular, quaternary ammonium compounds. Preferred cationicsurfactants are ammonium halides, more especially chlorides andbromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethylammonium chlorides and trialkyl methyl ammonium chlorides, for examplecetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride,distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride,lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammoniumchloride. In addition, the readily biodegradable quaternary estercompounds, so-called “esterquats”, for example the methyl hydroxyalkyldialkoyloxyalkyl ammonium methosulfates marketed under the registerednames of Dehyquart® and Stepantex®, may also be used.

Alkylamidoamines, more particularly fatty acid amidoamines, such as thestearylamidopropyl dimethyl amine commercially available under the nameof Tego Amid® S 18, are distinguished not only by their favorableconditioning effect, but also and in particular by their readybiodegradability.

In addition, it can be of advantage to color the individual phases withdyes in order to provide the preparation with a particularly favorableappearance. These dyes are preferably soluble only in the aqueous phaseor only in at least one non-aqueous phase in a quantity which makes thecorresponding coloration visible to the observer. It is also possible tocolor both the non-aqueous phase and the aqueous phase with differentdyes, preferably in different colors. However, it is preferred only tocolor a non-aqueous phase.

Other typical ingredients of the preparations according to the inventionare:

-   -   anionic surfactants such as, for example, soaps, alkyl sulfates        and alkyl polyglycol ether sulfates, salts of ether carboxylic        acids corresponding to the formula R—O—(CH₂CH₂O)_(x)—CH₂—COOH,        in which R is a linear alkyl group containing 10 to 22 carbon        atoms and x=0 or 1 to 16, acyl sarcosides, acyl taurides, acyl        isethionates, sulfosuccinic acid mono- and dialkyl esters,        linear alkane sulfonates, linear alpha-olefin sulfonates,        alpha-sulfofatty acid methyl esters and esters of tartaric acid        and citric acid, alkyl glycosides or alcohols which are products        of the addition of about 2 to 15 molecules of ethylene oxide        and/or propylene oxide onto fatty alcohols containing 8 to 22        carbon atoms.    -   zwitterionic surfactants such as, for example, betaines and        2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines.    -   ampholytic surfactants such as, for example, N-alkyl glycines,        N-alkyl propionic acids, N-alkyl aminobutyric acids,        N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl        glycines, N-alkyl taurines, N-alkyl sarcosines,        2-alkylaminopropionic acids and alkylaminoacetic acids.    -   nonionic surfactants such as, for example, products of the        addition of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of        propylene oxide onto linear fatty alcohols containing 8 to 22        carbon atoms, onto fatty acids containing 12 to 22 carbon atoms        and onto alkylphenols containing 8 to 15 carbon atoms in the        alkyl group, C₁₂₋₂₂ fatty acid monoesters and diesters of        addition products of 1 to 30 mol of ethylene oxide with        glycerol, C₈₋₂₂ alkyl monoglycosides and oligoglycosides and        ethoxylated analogs thereof and addition products of 5 to 60 mol        of ethylene oxide with castor oil and hydrogenated castor oil.    -   nonionic polymers such as, for example, vinyl pyrrolidone/vinyl        acrylate copolymers, polyvinyl pyrrolidone and vinyl        pyrrolidone/vinyl acetate copolymers,    -   anionic polymers such as, for example, polyacrylic and        polymethacrylic acids, salts thereof, copolymers thereof with        acrylates and methacrylates and acrylic and methacrylic acid        amides and derivatives thereof obtained by crosslinking with        polyfunctional agents, polyoxycarboxylic acids, such as        polyketo- and polyaldehydocarboxylic acids and salts thereof,        and polymers and copolymers of crotonic acid with esters and        amides of acrylic and methacrylic acid, such as vinyl        acetate/crotonic acid and vinyl acetate/vinyl        propionate/crotonic acid copolymers,    -   organic thickeners, such as agar agar, guar gum, alginates,        cellulose ethers, such as methyl and methyl hydroxypropyl        cellulose, gelatine, pectins and/or xanthan gum. Ethoxylated        fatty alcohols, particularly narrow-range types, for example the        product commercially available as Arlypon® (HENKEL), alkoxylated        methyl glucoside esters, such as the commercial product        Glucamate® DOE 120 (Amerchol), and ethoxylated propylene glycol        esters, such as the commercial product Antil® 141 (Goldschmidt),        can be preferred organic thickeners,    -   structurants, such as glucose and maleic acid,    -   hair-conditioning compounds, such as phospholipids, for example        soya lecithin, egg lecithin and kephalins,    -   perfume oils,    -   solubilizers, such as ethanol, isopropanol, ethylene glycol,        propylene glycol, glycerol, diethylene glycol and ethoxylated        triglycerides and also fatty alcohol ethoxylates and derivatives        thereof,    -   antidandruff agents, such as Climbazol, Piroctone Olamine and        Zinc Omadine,    -   active substances, such as bisabolol, allantoin, panthenol,        niacinmid, tocopherol and plant extracts,    -   UV filters,    -   consistency factors, such as sugar esters, polyol esters or        polyol alkyl ethers,    -   fats and waxes, such as spermaceti, beeswax, montan wax,        paraffins, esters, glycerides and fatty alcohols,    -   fatty acid alkanolamides,    -   complexing agents, such as EDTA, NTA, β-alanine diacetic acid        and phosphonic acids,    -   swelling and penetration agents, such as PCA, glycerol,        propylene glycol monoethyl ether, carbonates, hydrogen        carbonates, guanidines, ureas and primary, secondary and        tertiary phosphates,    -   opacifiers, such as latex or styrene/acrylamide copolymers,    -   pearlescers, such as ethylene glycol mono- and distearate or        PEG-3 distearate,    -   substantive dyes and    -   propellents, such as propane/butane mixtures, N₂O, dimethyl        ether, CO₂ and air.

Information on the other ingredients of the preparations according tothe invention and the quantities in which they are normally used can befound in known monographs, for example Umbach, Kosmetik, 2nd Edition,Georg Thieme Verlag, Stuttgart/New York, 1995 and Kh. Schrader,Grundlagen und Rezepturen der Kosmetika, 2nd Edition, Hüthig BuchVerlag, Heidelberg, 1989.

The following Examples are intended to illustrate the invention.

EXAMPLES

All quantities are in parts by weight unless otherwise indicated.

1. Mildly Alkaline Wave Lotion (Two Phases)

Invention Comparison Ammonium thioglycolate (71% in water) 16.0 16.0Ammonium hydrogen carbonate 6.0 6.0 Lamepon ® S¹ 0.8 0.8 Nutrilan ® KW²0.5 0.5 Natrosol ® 250 HR³ 0.15 0.15 Soybean oil 3.0 — Paraffin oil 35cP 10.0 — Apricot kernel oil 2.0 — Perfume oil 0.2 0.2 Ammonia (25% inwater) to pH 8.2 to pH 8.2 Water to 100 to 100 ¹Collagenhydrolyzate/cocofatty acid condensate, sodium salt (ca. 32% activesubstance in water; INCI name: Potassium Cocoyl Hydrolyzed Collagen)(HENKEL) ²Keratin hydrolyzate (20% active substance in water; INCI name:Hydrolyzed Keratin) (HENKEL) ³Hydroxyethyl cellulose (INCI name:Hydroxyethylcellulose) (HERCULES)

The wave lotion according to the invention had two phases (oil phase,water phase). The wave lotion according to the invention produced adistinctly better waving result than the one-phase wave lotion of theComparison Example. In addition, the hair had a particularly “cared-for”appearance. It was smoother and had a particularly good feel.

2. Neutral Wave Lotion (Two Phases)

Invention Comparison Ammonium thioglycolate (71% in water) 18.0 18.0Thiolactic acid 5.0 5.0 Imidazole 5.0 5.0 Eumulgin ® L⁴ 0.8 0.8Propylene glycol 0.7 0.7 Kollaplex ® 1.0-S⁵ 0.3 0.3 Soybean oil 8.5 —Avocado oil 1.5 — Perfume oil 0.4 0.4 Ammonia (235% in water) to pH 7.5to pH 75 Water to 100 to 100 ⁴2-Hydroxyfatty alcohol ethoxylate (INCIname: PPG-1-PEG-9-Lauryl Glycol Ether) (HENKEL) ⁵Collagen fixed topolysaccharides (INCI name; Soluble Collagen) (GfN)

The wave lotion according to the invention had two phases (oil phase,water phase). The wave lotion according to the invention produced adistinctly better waving result than the one-phase wave lotion of theComparison Example. In addition, the hair looked particularly cared-for.

3. Wave Lotion (Two Phases)

Ammonium thioglycolate (71% in water) 16.0 Ammonium hydrogen carbonate5.5 Lamepon ® S 1.4 Monomuls ® 90 O 18⁶ 1.4 Natrosol ® 250 HR 0.3Merquat ® 100⁷ 0.3 Gluadin ® WQ⁸ 0.5 Soybean oil 5.0 Perfume oil 0.3Ammonia (25% in water) to pH 8.4 Water to 100 ⁶Glycerol monooleate (INCIname: Glyceryl Oleate) (HENKEL) ⁷Poly(dimethyl diallyl ammoniumchloride) (40% active substance; INCI name: Polyquaternium-6)(CHEMVIRON) ⁸Quaternized wheat protein hydrolyzate (ca. 33% activesubstance in water; INCI name: Lauryldimonium Hydroxypropyl HydrolyzedWheat Protein) (GRÜNAU)4. Wave Lotion (Three Phases)

Ammonium thioglycolate (71% in water) 16.0 Ammonium hydrogen carbonate5.5 Lamepon ® S 1.4 Natrosol ® 250 HR 0.3 Merquat ® 100 0.3 Gluadin ® WQ0.5 Soybean oil 5.0 Dow Corning ® 344⁹ 5.0 Perfume oil 0.3 Ammonia (25%in water) to pH 8.4 Water to 100 ⁹Octamethyl cyclotetrasiloxane (INCIname: Cyclomethicone) (DOW CORNING)5. Wave Lotion (Two Phases)

Ammonium thioglycolate (71% in water) 16.0 Ammonium hydrogen carbonate9.0 Lamepon ® S 1.0 Merquat ® 100 0.5 Gluadin ® WQ 0.52-Ethylhexane-1,3-diol 5.0 Dye 0.0002 Perfume oil 1.0 Ammonia (25% inwater) to pH 8.4 Water to 100

The wave lotion produced intensive uniform waves with considerablebounce. The hair looked very cared-for after the treatment and was easyto comb.

6. Intermediate Rinse

Dioctyl carbonate 5.0 Paraffin oil 2.0 Water 93.0

By applying the intermediate rinse, the hair was easy to comb and lookedvery cared-for after the treatment.

7. Fixing Lotion (Three Phases)

Hydrogen peroxide (50% in water) 4.0 Aromox ® MCD-W¹⁰ 1.0 Turpinal ®SL¹¹ 1.0 Dioctyl carbonate 5.0 Paraffin oil 2.0 2-Ethylhexane-1,3-diol5.0 Water 82.0 ¹⁰N,N-dimethyl-N-cocoalkylamine-N-oxide (30% activesubstance in water; INCI name: Cocamine Oxide) (AKZO)¹¹1-Hydroxyethane-1,1-diphosphonic acid (ca. 60% active substance inwater; INCI name: Etidronic Acid) (HENKEL)

After the fixing treatment according to the invention, the hair was veryeasy to comb and looked very “cared-for”.

8. Wave Lotion for Porous Hair (Two Phases)

Ammonium thioglycolate (71% in water) 10.0 Ammonium hydrogen carbonate3.0 Lamepon ® S 1.0 Merquat ® 100 0.5 Gluadin ® WQ 0.52-Ethylhexane-1,3-diol 4.0 Dye 0.0001 Perfume oil 1.0 Imidazole 5.0Water to 100

The wave lotion produced intensive uniform waves with considerablebounce in porous hair. The hair looked very cared-for and was easy tocomb after the treatment.

9. Multicomponent Wave Lotion (Two Phases)

Component A (two phases) Ammonium bicarbonate 6.0 Ammonia 1.02-Ethylhexane-1,3-diol 10.0 Perfume 1.0 Merquat ® 100 0.1 Croquat ®WKP¹² 0.1 Water to 100.0 ¹²Quaternized keratin hydrolyzate (ca. 32%active substance in water; INCI name: Cocodimonium HydroxypropylHydrolyzed Keratin) (CRODA)

Component B Ammonium thioglycolate (71% in water) 50 Ammoniumthiolactate (70% in water) 25 Water to 100

Before use, 52 ml of component A was mixed with 23 ml of component B.The ready-to-use mixture formed was only temporarily homogeneous andvisibly separated into two phases after a few minutes. The wave lotionproduced intensive uniform waves with considerable bounce. The hairlooked very cared-for and was easy to comb after the treatment.

10. Heat-Activated 2-Component Wave Lotion for Porous Hair (Two Phases)

Component A (two phases) Ammonium thioglycolate (71% in water) 21.7Ammonia 2.8 2-Ethylhexane-1,3-diol 8.0 Perfume 1.0 Merquat ® 100 2.5Lamepon ® S 1.0 Water to 100

Component B hydrogen peroxide 50% 7.2 Phosphoric acid 85% 0.15 PHBmethyl ester 0.04 Water to 100

Before use, 60 ml of component A was mixed with 15 ml of component B.The ready-to-use mixture formed, of which the temperature was 15 to 20°C. higher than before mixing, was only temporarily homogeneous andvisibly separated into two phases after a few minutes. The wave lotionproduced intensive uniform waves with considerable bounce in poroushair. The hair looked very cared-for and was easy to comb after thetreatment.

1. A process for permanently deforming keratin fibers comprising thesteps of: (a) contacting keratin fibers with a reducing composition fora first contact time, wherein the reducing composition comprises atleast one keratin-reducing substance and is applied before or after, orbefore and after mechanically deforming the keratin fibers; (b) rinsingthe keratin fibers with a first rinse after the first contact time; (c)contacting the keratin fibers for a second contact time with a fixingcomposition comprising an oxidizing agent for fixing the keratin fibers,wherein at least one of the reducing composition, the fixing compositionor the first rinse is in the form of a two-phase or multiphase systemand comprises at least one alcohol having 4 to 10 carbon atoms andhaving only limited miscibility with water, and wherein the two phase ormultiphase system is capable of being converted by mechanical agitationinto a homogeneous system for application to the fibers; and (d) rinsingthe keratin fibers with a second rinse after the second contact time. 2.The process of claim 1, wherein the two phase or multiphase systemfurther comprises at least one oil.
 3. The process of claim 2 whereinthe oil is selected from one or more vegetable oils, paraffin oils orsilicones, or combinations thereof.
 4. The process of claim 3 whereinthe alcohol having only limited miscibility with water comprises a diolor trial.
 5. The process of claim 1 wherein the alcohol having onlylimited miscibility with water comprises a diol or triol.
 6. The processof claim 1 wherein the alcohol having only limited miscibility withwater is branched.